CN116314794A - Layered porous lithium battery conductive material, preparation method, conductive agent and battery - Google Patents
Layered porous lithium battery conductive material, preparation method, conductive agent and battery Download PDFInfo
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of conductive materials, and discloses a layered porous lithium battery conductive material, a preparation method, a conductive agent and a battery. The porous carbon precursor is based on the Mxene two-dimensional layered material, a layer-by-layer stacked structure of the Mxene and the graphene is constructed in a mode of compounding and drying with a dispersion liquid of the graphene oxide, and then the porous layered carbon structure and the graphene layer-by-layer assembled two-dimensional layered composite structure are obtained through the high-temperature reduction and etching processes. The structure of the invention simultaneously comprises a graphene layer with complete structure and high efficient conduction, and the porous lamellar carbon with good electrolyte wettability and excellent ion transmission performance. The composite material has excellent ion transmission and electron transmission characteristics, and is applied to lithium batteries, and the performance is far better than that of conductive carbon black, carbon nano tubes and graphene. Practical tests show that the battery internal resistance, high-rate charge-discharge performance and high-rate cycle performance of the lithium battery using the conductive agent are better than those of the existing product.
Description
Technical Field
The invention belongs to the technical field of conductive materials, and particularly relates to a layered porous lithium battery conductive material, a preparation method, a conductive agent and a battery.
Background
The conductive agent is a key auxiliary material of the lithium ion battery, and the positive electrode material of the lithium ion battery is usually a semiconductor or an insulator, so that the conductivity is low, and the addition of the conductive agent can increase the conductivity between active substances, reduce the contact resistance of electrodes and accelerate the electron movement rate, thereby improving the rate capability of the battery and prolonging the cycle life.
The current commonly used conductive agents mainly comprise carbon black, conductive graphite, VGCF (vapor grown carbon fiber), carbon nano tube, graphene and the like. Among them, carbon black, conductive graphite and VGCF belong to conventional conductive agents, and can form a conductive network of point, surface or line contact type between active materials. Carbon nanotubes and graphene belong to a novel conductive agent, wherein the carbon nanotubes form a line contact type conductive network between active substances; the graphene forms a surface contact conductive network between the active materials.
The graphene can form a surface contact type conductive network between active substances, so that a better conductive effect can be realized with a smaller addition amount. However, as graphene is easy to agglomerate and re-stack and has a compact structure, the ionic transmission in the charging and discharging processes of the lithium battery can be influenced in the practical application of the graphene in the lithium battery conductive agent, and the practical use effect is further influenced.
Therefore, it is necessary to develop a conductive material for efficient electron and ion transport based on graphene.
Through the above analysis, the problems and defects existing in the prior art are as follows: the existing improvement of the ion transmission capability of graphene is generally realized by constructing a defect for ion transmission on the surface of graphene, and the mode can improve certain ion transmission capability, but also greatly influences the structural integrity and the conductivity of graphene. In addition, a carbon precursor grows on the surface of graphene, and then a composite structure of graphene and porous carbon is constructed through carbonization and graphitization processes. However, the structure is generally in the form that punctate porous carbon grows on the surface of the flaky graphene, and the conductivity and the ion transmission property of the punctate porous carbon are also limited greatly.
Disclosure of Invention
In order to overcome the problems in the related art, the disclosed embodiments of the invention provide a layered porous lithium battery conductive material, a preparation method, a conductive agent and a battery, and in particular relates to a layered porous lithium battery conductive material based on Mxene and graphene.
The technical scheme is as follows: a layered porous lithium battery conductive material based on Mxene and graphene is prepared by taking Mxene two-dimensional layered material as a porous carbon precursor, constructing a layer-by-layer stacked structure of Mxene and graphene by compounding and drying with a dispersion liquid of graphene oxide, and then obtaining a two-dimensional layered composite structure formed by assembling a porous layered carbon structure and graphene layer by layer through high-temperature reduction and etching processes.
The invention further aims to provide a preparation method of the layered porous lithium battery conductive material based on Mxene and graphene, which comprises the following steps:
s1, preparing an Mxene dispersion liquid;
s2, preparing composite powder;
s3, reducing the composite powder to reduce the graphene oxide with a multi-layer composite structure into graphene;
and S4, etching the Mxene layer to form a porous carbon structure, and obtaining the layered porous conductive material.
In one embodiment, in step S1, preparing the Mxene dispersion comprises: using HCl/LiF to Ti 3 AlC 2 And etching and layering to prepare the MXene dispersion liquid.
In one embodiment, the resulting MXene dispersion specifically comprises the steps of:
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:10-40, the molar concentration of HCl in the HCl solution is 9M, and the stirring time is 20-120min;
and then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1: 10-100, the reaction temperature is 20-60 ℃ and the reaction time is 12-48h;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
In one embodiment, in step S2, preparing the composite powder includes: uniformly mixing the aqueous graphene oxide slurry and the Mxene dispersion liquid, and then obtaining the Mxene/graphene oxide composite powder through a spray drying process, wherein the Mxene and the graphene oxide are stacked between layers to form a multilayer composite structure in the spray drying process.
In one embodiment, the aqueous graphene oxide concentration is 0.1-1mg/ml; the ratio of graphene oxide to MXene is 1:0.5-2.
In one embodiment, in step S3, the composite powder is reduced in a hydrogen atmosphere at 500-800 ℃ for 1-8 hours, so that the graphene oxide of the multi-layer composite structure is reduced to graphene.
In one embodiment, in step S4, etching the Mxene layer to form the porous carbon structure includes: and introducing chlorine into the composite powder after heat treatment for etching for 2-8 hours to completely remove Ti and Al metal elements in the Mxene, thereby obtaining a porous carbon structure and finally obtaining the layered porous conductive material.
The invention further aims to provide a layered two-dimensional structured conductive agent which is prepared by using the layered porous lithium battery conductive material based on Mxene and graphene.
Another object of the present invention is to provide a lithium ion battery prepared using the layered two-dimensional structured conductive agent.
By combining all the technical schemes, the invention has the advantages and positive effects that:
first, aiming at the technical problems existing in the prior art and the difficulty of solving the problems, the technical problems solved by the technical scheme of the invention to be protected, results and data in the research and development process and the like are closely combined, the technical problems solved by the technical scheme of the invention are analyzed in detail and deeply, and some technical effects with creativity brought after the problems are solved are specifically described as follows:
the invention is based on the Mxene two-dimensional layered material as a porous carbon precursor, a structure of stacking Mxene and graphene layer by layer is constructed by compounding and drying with a dispersion liquid of graphene oxide, and then a two-dimensional layered composite structure of a porous layered carbon structure and graphene layer by layer is obtained by high-temperature reduction and etching processes. The composite material has excellent ion transmission and electron transmission characteristics, and is applied to lithium batteries, and the performance is far better than that of conductive carbon black, carbon nano tubes and graphene.
Secondly, the technical proposal is regarded as a whole or from the perspective of products, and the technical proposal to be protected has the technical effects and advantages as follows:
the layered two-dimensional structure can be simultaneously contacted with more electrode active material particles compared with point contact of conductive carbon black and linear contact of carbon nano tubes in the conductive agent, so that the effect of better improving the internal resistance of the battery pole piece can be exerted with smaller additive amount compared with the conductive carbon black and the carbon nano tubes.
The layered porous conductive material has a graphene structure with complete and high-conductivity compact layered structure and a porous layered structure which is porous and convenient for ion transmission. The conductive agent is applied to the lithium ion battery conductive agent, and can simultaneously give consideration to high-efficiency electronic conduction and ion conduction required by the high-rate charge and discharge process of the lithium ion battery, especially the power battery, so as to achieve the optimal conductive effect.
Practical tests show that the layered porous lithium battery conductive material can be used in a lithium battery, can obviously improve the internal resistance of the battery, and can reduce the polarization effect of high-rate charge and discharge of the lithium battery, so that the high-rate charge and discharge performance of the battery can be improved, and meanwhile, the cycle life of the high-rate charge and discharge process of the battery can be obviously prolonged. The lithium ion battery has important significance for lithium ion power batteries, in particular for new energy automobiles: the battery can realize faster charge and discharge speed, shortens the charge time and prolongs the service life of the battery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure;
fig. 1 is a flowchart of a preparation method of a layered porous lithium battery conductive material based on Mxene and graphene provided by an embodiment of the invention.
Fig. 2 is a scanning electron microscope image of a layered porous structure provided in an embodiment of the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
1. Explanation of the examples:
as shown in fig. 1, the embodiment of the invention provides a preparation method of a layered porous lithium battery conductive material based on Mxene and graphene, which comprises the following steps:
s1, preparing an Mxene dispersion liquid: using HCl/LiF to Ti 3 AlC 2 Etching and layering to prepare MXene dispersion;
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:10-40, the HCl concentration in the HCl solution is 9M (mol/L), and the stirring time is 20-120min;
then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1: 10-100, the reaction temperature is 20-60 ℃ and the reaction time is 12-48h;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
S2, preparing composite powder: uniformly mixing the aqueous graphene oxide slurry with the Mxene dispersion liquid, wherein the concentration of the aqueous graphene oxide is 0.1-1mg/ml. The ratio of graphene oxide to MXene is in the range of 1:0.5-2. Then, obtaining Mxene/graphene oxide composite powder through a spray drying process, wherein Mxene and graphene oxide are stacked between layers to form a multilayer composite structure in the spray drying process;
s3, reduction: placing the composite powder in a hydrogen atmosphere at 500-800 ℃ for reduction for 1-8h, so that graphene oxide with a multi-layer composite structure is reduced into graphene;
s4, etching the Mxene layer to form a porous carbon structure: and introducing chlorine into the composite powder after heat treatment to etch for 2-8 hours, so that Ti and Al metal elements in the Mxene are completely removed, and a porous carbon structure is obtained. And finally obtaining the layered porous conductive material.
The embodiment of the invention also provides a layered porous lithium battery conductive material based on Mxene and graphene, wherein the Mxene two-dimensional layered material is used as a porous carbon precursor, a layered structure of Mxene and graphene is constructed by compounding and drying a dispersion liquid of graphene oxide, and then a two-dimensional layered composite structure formed by assembling a porous layered carbon structure and graphene layer by layer is obtained by high-temperature reduction and etching processes. The scanning electron microscope photograph of the obtained layered porous structure is shown in fig. 2.
The following detailed description of the embodiments
Example 1
S1, preparing an Mxene dispersion liquid: using HCl/LiF to Ti 3 AlC 2 Etching and layering to prepare MXene dispersion;
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:10, the HCl concentration in the HCl solution is 9M (mol/L), and the stirring time is 120min;
then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1:50, the reaction temperature is 50 ℃, and the reaction time is 48 hours;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
S2, preparing composite powder: the aqueous graphene oxide slurry and the Mxene dispersion are uniformly mixed, and the concentration of the aqueous graphene oxide is 0.1mg/ml. The ratio of graphene oxide to MXene is 1:1. Then, obtaining Mxene/graphene oxide composite powder through a spray drying process, wherein Mxene and graphene oxide are stacked between layers to form a multilayer composite structure in the spray drying process;
s3, reduction: placing the composite powder in a hydrogen atmosphere at 800 ℃ for reduction for 8 hours, so that graphene oxide with a multi-layer composite structure is reduced into graphene;
s4, etching the Mxene layer to form a porous carbon structure: and introducing chlorine into the composite powder after heat treatment for etching for 8 hours, so that Ti and Al metal elements in the Mxene are completely removed, and a porous carbon structure is obtained. And finally obtaining the layered porous conductive material.
Example 2
S1, preparing an Mxene dispersion liquid: using HCl/LiF to Ti 3 AlC 2 Etching and layering to prepare MXene dispersion;
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:40, the HCl concentration in the HCl solution is 9M (mol/L), and the stirring time is 20min;
then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1:10, the reaction temperature is 20 ℃ and the reaction time is 12 hours;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
S2, preparing composite powder: and uniformly mixing the aqueous graphene oxide slurry with the Mxene dispersion liquid, wherein the concentration of the aqueous graphene oxide is 1mg/ml. The ratio of graphene oxide to MXene is 1:0.5. Then, obtaining Mxene/graphene oxide composite powder through a spray drying process, wherein Mxene and graphene oxide are stacked between layers to form a multilayer composite structure in the spray drying process;
s3, reduction: placing the composite powder in a hydrogen atmosphere at 500 ℃ for reduction for 8 hours, so that graphene oxide with a multi-layer composite structure is reduced into graphene;
s4, etching the Mxene layer to form a porous carbon structure: and introducing chlorine into the composite powder after heat treatment for etching for 2 hours, so that Ti and Al metal elements in the Mxene are completely removed, and a porous carbon structure is obtained. And finally obtaining the layered porous conductive material.
Example 3
S1, preparing an Mxene dispersion liquid: using HCl/LiF to Ti 3 AlC 2 Etching and layering to prepare MXene dispersion;
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:10, the HCl concentration in the HCl solution is 9M (mol/L), and the stirring time is 120min;
then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1:50, the reaction temperature is 50 ℃, and the reaction time is 48 hours;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
S2, preparing composite powder: the aqueous graphene oxide slurry and the Mxene dispersion are uniformly mixed, and the concentration of the aqueous graphene oxide is 0.1mg/ml. The ratio of graphene oxide to MXene is 1:2. Then, obtaining Mxene/graphene oxide composite powder through a spray drying process, wherein Mxene and graphene oxide are stacked between layers to form a multilayer composite structure in the spray drying process;
s3, reduction: placing the composite powder in a hydrogen atmosphere at 650 ℃ for reduction for 1h, so that graphene oxide with a multi-layer composite structure is reduced into graphene;
s4, etching the Mxene layer to form a porous carbon structure: and introducing chlorine into the composite powder after heat treatment for etching for 6 hours, so that Ti and Al metal elements in the Mxene are completely removed, and a porous carbon structure is obtained. And finally obtaining the layered porous conductive material.
Example 4
S1, preparing an Mxene dispersion liquid: using HCl/LiF to Ti 3 AlC 2 Etching and layering to prepare MXene dispersion;
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:20, the HCl concentration in the HCl solution is 9M (mol/L), and the stirring time is 60min;
then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1:20, the reaction temperature is 60 ℃ and the reaction time is 24 hours;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
S2, preparing composite powder: the aqueous graphene oxide slurry and the Mxene dispersion are uniformly mixed, and the concentration of the aqueous graphene oxide is 0.5mg/ml. The ratio of graphene oxide to MXene is 1:0.8. Then, obtaining Mxene/graphene oxide composite powder through a spray drying process, wherein Mxene and graphene oxide are stacked between layers to form a multilayer composite structure in the spray drying process;
s3, reduction: placing the composite powder in a hydrogen atmosphere at 700 ℃ for reduction for 6 hours, so that graphene oxide with a multi-layer composite structure is reduced into graphene;
s4, etching the Mxene layer to form a porous carbon structure: and introducing chlorine into the composite powder after heat treatment for etching for 4 hours, so that Ti and Al metal elements in the Mxene are completely removed, and a porous carbon structure is obtained. And finally obtaining the layered porous conductive material.
Example 5
S1, preparing an Mxene dispersion liquid: using HCl/LiF to Ti 3 AlC 2 Etching and layering to prepare MXene dispersion;
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:30, the HCl concentration in the HCl solution is 9M (mol/L), and the stirring time is 90min;
then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1:30, the reaction temperature is 40 ℃ and the reaction time is 18 hours;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
S2, preparing composite powder: the aqueous graphene oxide slurry and the Mxene dispersion are uniformly mixed, and the concentration of the aqueous graphene oxide is 0.8mg/ml. The ratio of graphene oxide to MXene is 1:1.5. Then, obtaining Mxene/graphene oxide composite powder through a spray drying process, wherein Mxene and graphene oxide are stacked between layers to form a multilayer composite structure in the spray drying process;
s3, reduction: placing the composite powder in a hydrogen atmosphere at 750 ℃ for reduction for 4 hours, so that graphene oxide with a multi-layer composite structure is reduced into graphene;
s4, etching the Mxene layer to form a porous carbon structure: and introducing chlorine into the composite powder after heat treatment for etching for 2 hours, so that Ti and Al metal elements in the Mxene are completely removed, and a porous carbon structure is obtained. And finally obtaining the layered porous conductive material.
Example 6
S1, preparing an Mxene dispersion liquid: using HCl/LiF to Ti 3 AlC 2 Etching and layering to prepare MXene dispersion;
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:40, the HCl concentration in the HCl solution is 9M (mol/L), and the stirring time is 40min;
then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1:100, the reaction temperature is 30 ℃ and the reaction time is 36h;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
S2, preparing composite powder: the aqueous graphene oxide slurry and the Mxene dispersion are uniformly mixed, and the concentration of the aqueous graphene oxide is 0.2mg/ml. The ratio of graphene oxide to MXene is 1:1. Then, obtaining Mxene/graphene oxide composite powder through a spray drying process, wherein Mxene and graphene oxide are stacked between layers to form a multilayer composite structure in the spray drying process;
s3, reduction: placing the composite powder in a hydrogen atmosphere at 550 ℃ for reduction for 7 hours, so that graphene oxide with a multi-layer composite structure is reduced into graphene;
s4, etching the Mxene layer to form a porous carbon structure: and introducing chlorine into the composite powder after heat treatment for etching for 5 hours, so that Ti and Al metal elements in the Mxene are completely removed, and a porous carbon structure is obtained. And finally obtaining the layered porous conductive material.
Example 7
S1, preparing an Mxene dispersion liquid: using HCl/LiF to Ti 3 AlC 2 Etching and layering to prepare MXene dispersion;
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:10, the HCl concentration in the HCl solution is 9M (mol/L), and the stirring time is 120min;
then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1:50, the reaction temperature is 50 ℃, and the reaction time is 48 hours;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
S2, preparing composite powder: the aqueous graphene oxide slurry and the Mxene dispersion are uniformly mixed, and the concentration of the aqueous graphene oxide is 0.1mg/ml. The ratio of graphene oxide to MXene is 1:3. Then, obtaining Mxene/graphene oxide composite powder through a spray drying process, wherein Mxene and graphene oxide are stacked between layers to form a multilayer composite structure in the spray drying process;
s3, reduction: placing the composite powder in a hydrogen atmosphere at 800 ℃ for reduction for 8 hours, so that graphene oxide with a multi-layer composite structure is reduced into graphene;
s4, etching the Mxene layer to form a porous carbon structure: and introducing chlorine into the composite powder after heat treatment for etching for 5 hours, so that Ti and Al metal elements in the Mxene are completely removed, and a porous carbon structure is obtained. And finally obtaining the layered porous conductive material.
Example 8
S1, preparing an Mxene dispersion liquid: using HCl/LiF to Ti 3 AlC 2 Etching and layering to prepare MXene dispersion;
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:10, the HCl concentration in the HCl solution is 9M (mol/L), and the stirring time is 120min;
then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1:50, the reaction temperature is 50 ℃, and the reaction time is 48 hours;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
S2, preparing composite powder: the aqueous graphene oxide slurry and the Mxene dispersion are uniformly mixed, and the concentration of the aqueous graphene oxide is 0.1mg/ml. The ratio of graphene oxide to MXene is 1:0.1. Then, obtaining Mxene/graphene oxide composite powder through a spray drying process, wherein Mxene and graphene oxide are stacked between layers to form a multilayer composite structure in the spray drying process;
s3, reduction: placing the composite powder in a hydrogen atmosphere at 800 ℃ for reduction for 8 hours, so that graphene oxide with a multi-layer composite structure is reduced into graphene;
s4, etching the Mxene layer to form a porous carbon structure: and introducing chlorine into the composite powder after heat treatment for etching for 5 hours, so that Ti and Al metal elements in the Mxene are completely removed, and a porous carbon structure is obtained. And finally obtaining the layered porous conductive material.
Comparative example 1
S1, preparing an Mxene dispersion liquid: using HCl/LiF to Ti 3 AlC 2 Etching and layering to prepare MXene dispersion;
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:10, the HCl concentration in the HCl solution is 9M (mol/L), and the stirring time is 120min;
then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1:50, the reaction temperature is 50 ℃, and the reaction time is 48 hours;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
S2, preparing powder: the Mxene supernatant is subjected to a spray drying process to obtain Mxene powder;
s3, etching Mxene to form a porous carbon structure: and introducing chlorine into the composite powder after heat treatment to etch for 2-8 hours, so that Ti and Al metal elements in the Mxene are completely removed, and a porous carbon structure is obtained. And finally obtaining the porous conductive material.
Comparative example 2
S1, preparing graphene oxide powder: carrying out a spray drying process on the aqueous graphene oxide slurry to obtain graphene oxide composite powder;
s2, reduction: placing graphene oxide powder in a hydrogen atmosphere at 800 ℃ for reduction for 1-8h, so that graphene oxide is reduced into graphene;
2. the technical scheme of the invention is further described below in connection with a performance test method.
The performance test method comprises the following steps:
1. preparation of battery pole piece
Positive active material lithium iron phosphate, conductive agent and binder (polytetrafluoroethylene)Ethylene, PVDF) according to 93.5:4.0:2.5, mixing with N-methyl pyrrolidone (NMP), stirring and dispersing to obtain positive slurry, coating, drying, grain pressing, die cutting, and making into positive plate. The density of the coated single surface is 190g/m 2 The density of the double-sided surface is 380g/m 2 . Graphite, a conductive agent, sodium methyl cellulose (CMC) and styrene butadiene rubber (SBR, 40% of solid content) are dispersed in deionized water according to the mass ratio of 96.0:1.0:1.5:1.5, and the mixture is fully stirred and mixed to form uniformly dispersed cathode slurry. The negative plate is manufactured through the procedures of coating, drying, rolling, die cutting and the like. The positive electrode coating substrate is carbon-coated aluminum foil, and the negative electrode coating substrate is copper foil.
2. The positive electrode plate and the diaphragm are manufactured into a dry battery core according to a lamination process, the battery diaphragm is a single-sided ceramic diaphragm, the negative electrode is one more than the positive electrode plate, and after the dry battery core is put into a shell, the lithium battery full battery is manufactured through baking, liquid injection, formation, aging and capacity division.
3. And obtaining the battery charge and discharge performance by testing a battery charge and discharge curve (voltage range is 2.5-3.6V), and obtaining the battery internal resistance by testing the battery alternating current impedance spectrum.
In the performance test method, the conductive agent is the layered porous conductive material, the porous carbon material or the graphene obtained in the embodiment of the invention and the comparative example; or a commonly used conductive agent for outsourced lithium batteries, namely conductive carbon black or carbon nanotubes.
The test data table is shown below:
from examples 1-6 (process in the scope of protection) and examples 7-8 (process slightly outside the scope of protection) the comparative examples were presented. Compared with the traditional graphene, conductive carbon black and carbon nanotube conductive agent, the conductive material provided by the invention can obviously reduce the internal resistance of the battery and improve the discharge median voltage of the battery, especially the high-rate discharge median voltage. Meanwhile, the cycle life of the battery under the condition of high-rate charge and discharge can be remarkably prolonged.
Practical tests show that the battery internal resistance, high-rate charge-discharge performance and high-rate cycle performance of the lithium battery using the conductive agent are better than those of the existing product.
3. The technical scheme of the invention is further described below with reference to application examples.
Application example 1
The embodiment of the invention provides a high-rate charge-discharge battery pack of a power battery, which is provided with the lithium ion battery, is arranged in a public transportation motor vehicle and conducts electrons and ions at low temperature.
Application example 2
The embodiment of the invention provides a working robot carrying the high-rate charge-discharge battery pack of the power battery.
While the invention has been described with respect to what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. The laminated porous lithium battery conductive material based on the Mxene and the graphene is characterized in that the laminated porous lithium battery conductive material based on the Mxene and the graphene takes a Mxene two-dimensional laminated material as a porous carbon precursor, a layer-by-layer stacked structure of the Mxene and the graphene is constructed by compounding and drying a dispersion liquid of the graphene oxide, and a two-dimensional laminated composite structure formed by assembling the porous laminated carbon structure and the graphene layer by layer is obtained by high-temperature reduction and etching processes.
2. A method for preparing the layered porous lithium battery conductive material based on Mxene and graphene according to claim 1, characterized in that the method comprises the following steps:
s1, preparing an Mxene dispersion liquid;
s2, preparing composite powder;
s3, reducing the composite powder to reduce the graphene oxide with a multi-layer composite structure into graphene;
and S4, etching the Mxene layer to form a porous carbon structure, and obtaining the layered porous conductive material.
3. The method according to claim 2, wherein in step S1, HCl/LiF is used for Ti 3 AlC 2 And etching and layering to prepare the MXene dispersion liquid.
4. The method according to claim 3, wherein the obtaining of the MXene dispersion comprises the steps of:
adding LiF into HCl solution, stirring and fully dissolving; the mass ratio of LiF to HCl solution is 1:10-40, the molar concentration of HCl in the HCl solution is 9M, and the stirring time is 20-120min;
and then Ti is added 3 AlC 2 Adding the mixture into the mixed solution in batches and fully stirring for reaction; ti (Ti) 3 AlC 2 The proportion of the mixed solution is 1: 10-100, the reaction temperature is 20-60 ℃ and the reaction time is 12-48h;
after complete reaction, deionized water is added for repeated washing until the pH value is 7; and then adding ethanol for cleaning, centrifuging for 10min at 10000r/min to remove supernatant, adding deionized water again, and centrifuging for 3min at 3500r/min to obtain a few-layer MXene supernatant.
5. The method according to claim 2, wherein in step S2, preparing the composite powder comprises: uniformly mixing the aqueous graphene oxide slurry and the Mxene dispersion liquid, and then obtaining the Mxene/graphene oxide composite powder through a spray drying process, wherein the Mxene and the graphene oxide are stacked between layers to form a multilayer composite structure in the spray drying process.
6. The method according to claim 5, wherein the concentration of the aqueous graphene oxide is 0.1-1mg/ml; the ratio of graphene oxide to MXene is 1:0.5-2.
7. The preparation method according to claim 2, wherein in step S3, the composite powder is reduced in a hydrogen atmosphere at 500-800 ℃ for 1-8 hours, so that the graphene oxide of the multi-layer composite structure is reduced to graphene.
8. The method of claim 2, wherein etching the Mxene layer to form the porous carbon structure in step S4 comprises: and introducing chlorine into the composite powder after heat treatment for etching for 2-8 hours to completely remove Ti and Al metal elements in the Mxene, thereby obtaining a porous carbon structure and finally obtaining the layered porous conductive material.
9. A layered two-dimensional structured conductive agent prepared using the Mxene and graphene-based layered porous lithium battery conductive material of claim 1.
10. A lithium ion battery prepared using the layered two-dimensional structured conductive agent of claim 7.
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| CN104701026A (en) * | 2015-01-28 | 2015-06-10 | 燕山大学 | Carbon-carbon composite electrode material and preparation method thereof |
| CN111799464A (en) * | 2020-07-08 | 2020-10-20 | 中国科学院电工研究所 | MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof |
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